Organic carboxylic acid salt composition, process for preparation thereof and additives for epoxy resins

ABSTRACT

The present invention provides an organic carboxylate composition that has long working life, cures epoxy resins, and improves adhesive properties, and also provides a method for producing the same. An organic carboxylate composition, obtained by heating and mixing a basic silane coupling agent and an amine compound with a softening point or melting point of 40° C. or greater together with an organic carboxylic acid; a method for producing the same; an additive for epoxy resin that contains this as the active ingredient thereof; and an epoxy resin composition containing the same. The basic silane coupling agent should preferably be a specific imidazole-group containing silane coupling agent, amino group-containing silane coupling agent, dialkylamino group-containing silane coupling agent, monomethylamino group-containing silane coupling agent, benzimidazole group-containing silane coupling agent, benzotriazole group-containing silane coupling agent, and pyridine ring-containing silane coupling agent.

TECHNICAL FIELD

The present invention relates to an organic carboxylate compositioncapable of exhibiting exceptional storage stability and enhancedadhesion as a coupling agent for powdered paints or as an additive forone-component epoxy resin compositions, and to a producing method andutilization thereof.

BACKGROUND ART

Imidazoles are curing agents that are receiving attention for providingexceptional curing properties to resin compositions, resulting in curedmaterials with high heat resistance. However, because of problems withstorage stability, extending working life by controlling basicity isbeing investigated through formation of metal complexes and varioustypes of acid salts. The inventors have filed patent applications(Japanese Patent Application Publication Nos. 9-12683 and 2000-297094)in which a mixture of the general formulas (1), (2), and (3) below or animidazole group-containing silane coupling agent expressed by thegeneral formula (4) would provide, as curing agents for epoxy resins,curable epoxy resin compositions having exceptional adhesion properties.However, these imidazole group-containing silane coupling agents aredisadvantageous in having poor storage stability in the same manner asdo conventional imidazoles.

Poor storage stability when mixed with epoxy resin is also a problemwith silane coupling agents such as amino group-containing silanecoupling agents (commercial products), dialkylamino group-containingsilane coupling agents (Japanese Patent Application Publication Nos.9-295988, 9-296135, and 9-295989), monomethylamino group-containingsilane coupling agents (commercial products), benzimidazolegroup-containing silane coupling agents (Japanese Patent ApplicationPublication No. 6-279458), benzotriazole group-containing silanecoupling agents (Japanese Patent Application Publication No. 6-279463),or pyridine ring-containing silane coupling agents (Japanese PatentApplication Publication Nos. 9-295990 and 9-295991).

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide an organic carboxylatecomposition that is solid at room temperature, remains stable and haslong working life when mixed with epoxy resin without compromising theimproved adhesion characteristics of the above-mentioned silane couplingagents with respect to appropriate epoxy resins, melts at a prescribedtemperature, and has silane coupling functionality capable ofcontributing to the curing reaction of the epoxy resins; to provide amethod for producing the same; and to provide an additive for epoxyresin and an epoxy resin composition containing the same.

As a result of extensive investigation, the inventors discovered that abasic silane coupling agent organic carboxylate composition obtained bya specific method not only had exceptional curing properties and storagestability as an additive for epoxy resin, but also yielded a significantenhancement to adhesion properties. The present invention is based uponthis discovery, and can be summarized as follows.

[1] An organic carboxylate composition, obtained by heating and mixing abasic silane coupling agent and an amine compound having a softeningpoint or melting point of 40° C. or greater together with an organiccarboxylic acid.

[2] A method for producing an organic carboxylate composition,comprising heating and mixing a basic silane coupling agent and an aminecompound having a softening point or melting point of 40° C. or greatertogether with an organic carboxylic acid.

[3] The organic carboxylate composition according to [1], wherein thebasic silane coupling agent is comprised of one compound or a mixture oftwo or more compounds selected from the group consisting of compoundsexpressed by the general formulas (1) through (4) below, or at least oneselected from the group consisting of amino group-containing-silanecoupling agents, dialkylamino group-containing silane coupling agents,monomethylamino group-containing silane coupling agents, benzimidazolegroup-containing silane coupling agents, benzotriazole group-containingsilane coupling agents, and pyridine ring-containing silane couplingagents.

wherein in the formulas (1) through (3), R¹, R², and R³ each representhydrogen, a vinyl group, or an alkyl group having 1 to 20 carbon atomsand R² and R³ may form an aromatic ring; R⁴ and R⁵ each represent analkyl group having 1 to 5 carbon atoms; and m and n are integers of 1 to10 and 1 to 3, respectively, and

wherein in the formula (4), R⁶, R⁷, and R⁸ each represent hydrogen, analkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group,or a benzyl group, and R⁷ and R⁸ may bond and form an aromatic ring; R⁹represents hydrogen or an alkyl group having 1 to 3 carbon atoms; R¹⁰and R¹¹ each represent an alkyl group having 1 to 5 carbon atoms; and oand p are integers of 1 to 10 and 1 to 3, respectively.

[4] A method for producing the organic carboxylate composition accordingto [2], wherein the basic silane coupling agent is comprised of onecompound or a mixture of two or more compounds selected from the groupconsisting of compounds expressed by the general formulas (1) through(4) below, or at least one of amino group-containing silane couplingagents, dialkylamino group-containing silane coupling-agents,monomethylamino group-containing silane coupling agents, benzimidazolegroup-containing silane coupling agents, benzotriazole group-containingsilane coupling agents, and pyridine ring-containing silane couplingagents.

wherein the respective symbols in the formulas are the same as thoseshown in [3] above.

[5] An epoxy resin composition, containing the organic carboxylatecomposition according to [1] or [3].

[6] An additive for epoxy resin, containing the organic carboxylatecomposition according to [1] or [3].

The present invention will be described in further detail hereafter.

The basic silane coupling agent used in the production of the organiccarboxylate composition of the present invention should preferably be asingle compound or a mixture of two or more compounds selected from thegroup consisting of compounds expressed by the general formulas (1)through (4) above, or at least one selected from the group consisting ofamino group-containing silane coupling agents, dialkylaminogroup-containing silane coupling agents, monomethylaminogroup-containing silane coupling agents, benzimidazole group-containingsilane coupling agents, benzotriazole group-containing silane couplingagents, and pyridine ring-containing silane coupling agents.

The compounds expressed by the general formulas (1) through (3) abovecan be synthesized based on the method disclosed in Japanese PatentApplication Publication No. 5-186479. The compound expressed by thegeneral formula (4) above can be synthesized based on the methoddisclosed in Japanese Patent Application Publication No. 2000-297094.The compounds of the general formulas (1) through (3) above can beobtained as mixtures in the manner described in Japanese PatentApplication Publication No. 5-186479, so there is no particular need toseparate the mixtures, and the compounds should preferably be used as-isin the form of such mixtures.

Amino group-containing silane coupling agents include(3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,(3-aminopropyl)dimethoxymethylsilane,(3-aminopropyl)diethoxymethylsilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and the like.Monomethylamino group-containing silane coupling agents includeN-methylaminopropyltrimethoxysilane, N-methylaminopropyltriethoxysilane,and the like. Dialkylamino group-containing silane coupling agentsinclude those disclosed in Japanese Patent Application Publication Nos.9-295988, 9-296135, and 9-295989. Among these, dimethylaminogroup-containing silane coupling agents are particularly preferred.Benzotriazole-containing silane coupling agents include those disclosedin Japanese Patent Application Publication No. 6-279463, benzimidazolegroup-containing silane coupling agents include those disclosed inJapanese Patent Application Publication No. 6-279458, and pyridinering-containing silane coupling agents include those disclosed inJapanese Patent Application Publication Nos. 9-295990 and 9-295991.

The organic carboxylate composition of the present invention is obtainedby a process in which the basic silane coupling agent and an aminecompound with a softening point or melting point of 40° C. or greaterare heated and mixed with an organic carboxylic acid at 50-200° C. Ifthe softening point or melting point is less than 40° C., the resultingproduct is less amenable to hardening, and the hardened product is lessamenable to pulverization.

Examples of amine compounds with a softening point or melting point of40° C. or greater include imidazole compounds, aromatic amines,aliphatic amines, dicyandiamides, organic acid hydrazides, and modifiedpolyamines. Specific Examples thereof are described in “RecentDevelopment of Epoxy Resin Hardener” (compiled under the supervision ofHiroshi Kakiuchi, published by CMC, 1994).

Examples of imidazole compounds include 1H imidazole, 2-methylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 1-benzyl-2-methylimidazole,2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,and 1-cyanoethyl-undecylimidazole.

An aliphatic saturated carboxylic acid, aliphatic unsaturated carboxylicacid, aromatic carboxylic acid, or the like can be used as the organiccarboxylic acid. Desirable organic carboxylic acids from among theseinclude maleic acid, itaconic acid, azelaic acid, phthalic acid, acrylicacid, methacrylic acid, isobutyric acid, octylic acid, formic acid,glyoxylic acid, crotonic acid, acetic acid, propionic acid, benzoicacid, salicylic acid, cyclohexanecarboxylic acid, toluic acid,phenylacetic acid, p-t-butylbenzoic acid, trimellitic acid, trimelliticanhydride, cis-4-cyclohexene dicarboxylic acid, 2-octenyl succinic acid,2-dodecenyl succinic acid, pyromellitic acid, and the like.

The reaction molar ratio of the basic silane coupling agent, the aminecompound with a softening point or melting point of 40° C. or greater,and the organic carboxylic acid should preferably be such that at leastone carboxyl group per mole of the organic carboxylic acid forms a saltwith a base. The molar ratio of the combined number of moles of thebasic silane coupling agent and the amine compound with a softeningpoint or melting point of 40° C. or greater, and the organic carboxylicacid should be 1:0.1 to 1:5, and preferably 1:0.2 to 1:2. The molarratio of the basic silane coupling agent and the amine compound with asoftening point or melting point of 40° C. or greater should beestablished such that the organic carboxylate composition obtained bythe heating and mixing procedure is in solid form at room temperature.The ratio is thus selected from a range of 5:1 to 1:5. The compositionis less likely to be in solid form at room temperature if the molarratio of the basic silane coupling agent exceeds this range, and theresulting silane coupling functions are inadequate if the molar ratio ofthe amine compound with a softening point or melting point of 40° C. orgreater exceeds this range.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples will be shown hereafter, and the present invention will bedescribed in further detail. In the Examples that follow, “parts”designates “parts by weight.”

Synthesis of Organic Carboxylate Composition

EXAMPLE 1

13.62 g (0.2 mol) of imidazole was melted at 95° C., and 47.27 g (0.2mol) of (3-glycidoxypropyl)trimethoxysilane was added dropwise theretoover a period of 30 minutes while stirred in an argon atmosphere.Following addition, the product was further reacted for one hour at atemperature of 95° C., yielding an imidaz,ole group-containing silanecoupling agent comprising a mixture of the compounds represented by thechemical formulas (1), (2), and (3) below. In the formulas (1), (2), and(3) below, R¹, R², and R³ are H; R⁴ is CH₃; n is 3; and m is 3. 2.16 g(0.04 mol) of the imidazole group-containing silane coupling agent thusobtained, 8.64 g (0.06 mol) of 2-phenylimidazole (melting point:137-147° C.), and 21.0 g (0.1 mol) of trimellitic acid were heated andmixed at 160° C., the reaction was continues for one hour, and theproduct was cooled to room temperatures, yielding an imidazoletrimellitate composition that was solid at normal temperature. The solidproduct thus obtained was ground with a mortar and classified by a sievewith hole openings of 90 microns to yield pulverized Sample No. 1.

EXAMPLE 2

13.6 g (0.2 mol) of imidazole and 24.8 g (0.1 mol) of(3-methacryloxypropyl)trimethoxysilane were mixed and reacted at 100° C.for 11 hours. After cooling to room temperature, 100 ml of ethyl acetatewas added, and excess imidazole was removed by washing the product threetimes in 100 ml of deionized water. Molecular sieves were added to theproduct, and the ethyl acetate solution was dried overnight.Subsequently, the ethyl acetate was distilled off in a rotaryevaporator, and the imidazole group-containing silane coupling agentexpressed by the formula (4) below was obtained. In the formula, R⁶, R⁷,and R⁸ are H; R⁹ is CH₃; R¹⁰ is CH₃; o is 3; and p is 3. 12.64 g (0.04mol) of the imidazole group-containing silane coupling agent thusobtained, 8.64 g (0.06 mol) of 2-phenylimidazole (melting point:137-147° C.), and 21.0 g (0.1 mol) of trimellitic acid were heated andmixed at 160° C., the reaction was continued for one hour, and theproduct was cooled to room temperature, yielding an imidazoletrimellitate composition that was solid at normal temperature. The solidproduct thus obtained was ground with a mortar and classified by a sievewith hole openings of 90 microns to yield pulverized Sample No. 2.

Evaluation of Adhesion Properties

EXAMPLE 3

Epoxy resin compositions containing Sample Nos. 1 and 2 obtained inExamples 1 and 2 were prepared, and the effect on adhesion propertieswas evaluated.

Epoxy Resin Composition:

Bisphenol A-type epoxy (Epikote 828, mfd. by Japan Epoxy Resins Co.,Ltd.): 100 parts by weight

Dicyandiamide (AH-154, mfd. by Ajinomoto Co., Inc.): 5 parts by weight

2-Ethyl-4-methylimidazole (2E4MZ, mfd. by Shikoku Chemicals Corp.): 1part by weight

Sample No. 1 or 2: 1 part by weight

Backing material: SUS304 (polished with No. 240 abrasive paper (inaccordance with JIS K6848) immediately before use, and used after beingcleaned with acetone) Dimensions 100×25×2 in thickness (mm)

Curing conditions: 100° C.×1 hour+150° C.×1 hour

Evaluation method: The epoxy resin composition was sandwiched betweentwo SUS304 backing sheets, and shear adhesive strength was measured at acrosshead speed of 1 mm/min by means of a tensile tester followingheating and curing (according to JIS K6850).

The evaluation results thus obtained are shown in Table 1.

COMPARATIVE EXAMPLES 1 AND 2

Epoxy resin compositions and bonded materials were prepared andevaluated as comparative examples in the same manner as in Example 3,except that the sample used in Example 3 was not added (ComparativeExample 1) and one part of (3-glycidoxypropyl)trimethoxysilane was added(Comparative Example 2) instead of the above-mentioned sample. Theobtained results are shown in Table 1.

TABLE 1 Effects of Adding Sample Nos. 1 and 2 on Shear Adhesive StrengthShear adhesive Additive strength(kN/cm²) Example 3 Sample No. 1 1.38Sample No. 2 1.36 Comparative No additive 1.02 Example 1 Comparative(3-glycidoxypropyl) 1.11 Example 2 trimethoxysilaneEvaluation of Mechanical Characteristics of Cured Material

EXAMPLE 4

An epoxy resin cured material containing each of Sample Nos. 1 and 2,which were obtained in Examples 1 and 2, was prepared, and the effect onmechanical characteristics was evaluated.

Epoxy Resin Composition:

Bisphenol A-type epoxy (Epikote 828, mfd. by Japan Epoxy Resins Co.,Ltd.): 100 parts by weight

Dicyandiamide (AH-154, mfd. by Ajinomoto Co., Inc.): 5 parts by weight

2-Ethyl-4-methylimidazole (2E4MZ, mfd. by Shikoku

Chemicals Corp.): 1 part by weight

Sample No. 1 or 2: 1 part by weight

Granular silica filler (RD-8, mfd. by Tatsumori K. K.): 100 parts byweight

Dimensions of cured material: 80×10×4 in thickness (mm)

Curing conditions: 100° C.×1 hour+150° C.×1 hour

Evaluation method: Three-point flexural strength was measured at acrosshead speed of 2 mm/min at the loading point (in accordance with JISK6911).

The evaluation results thus obtained are shown in Table 2.

COMPARATIVE EXAMPLES 3 AND 4

Epoxy resin cured materials were prepared and evaluated as comparativeexamples in the same manner as in Example 4, except that the sample usedin Example 4 was not added (Comparative Example 3) and one part of(3-glycidoxypropyl)trimethoxysilane was added (Comparative Example 4)instead of the above-mentioned sample. The results are shown in Table 2.

TABLE 2 Effects of Adding Sample Nos. 1 and 2 on Flexural Strength ofCured Materials Flexural strength Additive (N/mm²) Example 4 Sample No.1 99.1 Sample No. 2 98.2 Comparative No additive 84.1 Example 3Comparative (3-glycidoxypropyl) 90.2 Example 4 trimethoxysilaneEvaluation of Storage Stability and Curing Acceleration

EXAMPLE 5

The epoxy resin composition shown below was prepared by adding each ofSample Nos. 1 and 2, and this composition was evaluated for storagestability on the basis of the viscosity change during storage at roomtemperature. Curing acceleration was also evaluated by measuring thegelation time on a hot plate that was set to 150° C. The results areshown in Table 3.

Epoxy Resin Composition:

Bisphenol A-type epoxy (Epikote 828, mfd. by Japan Epoxy Resins Co.,Ltd.): 100 parts by weight

Dicyandiamide (AH-154, mfd. by Ajinomoto Co., Inc.): 5 parts by weight

Sample No. 1 or 2: 5 parts by weight

COMPARATIVE EXAMPLES 5 AND 6

Epoxy resin compositions were prepared and evaluated as comparativeexamples in the same manner as in Example 5, except that one part of2-ethyl-4-methylimidazole (2E4MZ, mfd. by Shikoku Chemicals Corp.) wasadded (Comparative Example 5) instead of Sample No. 1 or 2 used inExample 5 and that the aforementioned samples were not added(Comparative Example 6). The evaluation results are shown in Table 3.

TABLE 3 Effects of Adding Sample Nos. 1 and 2 on Storage Stability ofEpoxy Resin Compositions Storage Curing stability acceleration(viscosity (gelation Additive change) time) Example 5 Sample No. 1 Noviscosity 10 min. and change during 23 sec. Sample No. 2 storage for  7min. and 54 sec. 10 days Comparative 2-ethyl-4- Hardened due  2 min. and11 sec. Example 5 methylimidazole to storage for 10 days Comparative Noadditive No viscosity 20 min. and Example 6 change during 28 sec.storage for 10 daysEvaluation of Heat Softening

EXAMPLE 6

The heat softening properties of Sample Nos. 1 and 2 were evaluatedusing a temperature-controlled hot plate. The results are shown in Table4.

TABLE 4 Evaluation of Heat Softening Properties of Sample Nos. 1 and 2Sample No. Heat softening temperature (° C.) 1 110° C. 2  90° C.Synthesis and Adhesion Evaluation of Organic Carboxylate

EXAMPLES 7-17

Organic carboxylate compositions were prepared and Sample Nos. 3-13 wereobtained in the same manner as in Example 1 except for the use of thebasic silane coupling agents, amine compounds with a softening point ormelting point of 40° C. or greater, and organic carboxylic acids shownin Table 5 below.

TABLE 5 Sample No. 3 (3-aminopropyl)trimethoxysilane: 0.04 mol2-Phenylimidazole (melting point: 137-147° C.): 0.06 mol Trimelliticacid: 0.1 mol 4 N-methylaminopropyltrimethoxysilane: 0.04 mol2-Phenylimidazole (melting point: 137-147° C.): 0.06 mol Trimelliticacid: 0.1 mol 5 Benzotriazole group-containing silane coupling agentsynthesized in Example 1 of Japanese Patent Application Publication No.6-279463: 0.04 mol 2-Phenylimidazole (melting point: 137-147° C.): 0.06mol Trimellitic acid: 0.1 mol 6 Dimethylaminosilane synthesized inReference Example 1 of Japanese Patent Application Publication No.9-296135: 0.04 mol 2-Phenylimidazole (melting point: 137-147° C.): 0.06mol Trimellitic acid: 0.1 mol 7 Benzimidazole group-containing silanecoupling agent synthesized in Example 1 of Japanese Patent ApplicationPublication No. 6-279458: 0.04 mol 2-Phenylimidazole (melting point:137-147° C.): 0.06 mol Trimellitic acid: 0.1 mol 8 Pyridinering-containing silane coupling agent synthesized in Example 1 ofJapanese Patent Application Publication No. 9-295991: 0.04 mol2-Phenylimidazole (melting point: 137-147° C.): 0.06 mol Trimelliticacid: 0.1 mol 9 Imidazole group-containing silane coupling agentobtained in the same manner as in Example 1: 0.04 mol Diaminodiphenylmethane (melting point 89° C.): 0.06 mol Trimellitic acid: 0.1 mol 10Imidazole group-containing silane coupling agent obtained in the samemanner as in Example 1: 0.04 mol Diaminodicyclohexyl methane (meltingpoint 40° C.): 0.06 mol Trimellitic acid: 0.1 mol 11 Imidazolegroup-containing silane coupling agent obtained in the same manner as inExample 1: 0.04 mol Dicyandiamide (melting point 207-210° C.): 0.06 molTrimellitic acid: 0.1 mol 12 Imidazole group-containing silane couplingagent obtained in the same manner as in Example 1: 0.04 mol Adipichydrazide (melting point 178° C.): 0.06 mol Trimellitic acid: 0.1 mol 13Imidazole group-containing silane coupling agent obtained in the samemanner as in Example 1: 0.04 mol Modified polyamine (polyaminoimideobtained from tetracarboxylic acid, ATI-2) (melting point 270° C.): 10 gTrimellitic acid: 0.1 mol

Using the samples thus obtained, epoxy resin compositions were producedand shear adhesive strength was evaluated in the same manner as inExample 3. The results are shown in Table 6 below.

TABLE 6 Shear adhesive Additive strength (kN/cm²) Example 7 Sample 31.24 Example 8 Sample 4 1.26 Example 9 Sample 5 1.20 Example 10 Sample 61.42 Example 11 Sample 7 1.40 Example 12 Sample 8 1.32 Example 13 Sample9 1.37 Example 14 Sample 10 1.30 Example 15 Sample 11 1.44 Example 16Sample 12 1.33 Example 17 Sample 13 1.28

INDUSTRIAL APPLICABILITY

The organic carboxylate composition of the present invention is solid atroom temperature and can function as a silane coupling agent.Applications thereof include not only functioning as an exceptionaladhesion enhancer when added to a one-component resin composition, butalso being able to impart long working life due to being solid at roomtemperature and having an organic carboxylate structure. The compositioncan also be pulverized and used in powdered coating materials becausethe heat softening temperature thereof is relatively high. In addition,the adhesiveness, mechanical properties, and storage stability of thecomposition allow this composition to be applied to the required epoxyresin compositions in a wide range of possible applications, includingadhesives, paints, laminates, molding, printed wiring boards,copper-clad laminates, resin-coated copper foil, semiconductor chipcoating materials, semiconductor chip mounting materials, photoresists,solder resists, dry film resists, and the like.

1. An organic carboxylate composition, obtained by heating and mixing abasic silane coupling agent and an amine compound having a softeningpoint or melting point of 40° C. or greater together with an organiccarboxylic acid.
 2. A method for producing an organic carboxylatecomposition, comprising heating and mixing a basic silane coupling agentand an amine compound having a softening point or melting point of 40°C. or greater together with an organic carboxylic acid.
 3. The organiccarboxylate composition according to claim 1, wherein the basic silanecoupling agent is comprised of one compound or a mixture of two or morecompounds selected from the group consisting of compounds expressed bythe general formulas (1) through (4) below, or at least one selectedfrom the group consisting of amino group-containing silane couplingagents, dialkylamino group-containing silane coupling agents,monomethylamino group-containing silane coupling agents, benzimidazolegroup-containing silane coupling agents, benzotriazole group-containingsilane coupling agents, and pyridine ring-containing silane couplingagents,

wherein in the formulas (1) through (3), R¹, R², and R³ each representhydrogen, a vinyl group, or an alkyl group having 2 to 20 carbon atomsand R² and R³ may form an aromatic ring; R⁴ and R⁵ each represent analkyl group having 1 to 5 carbon atoms; and m and n are integers off 1to 10 and 1 to 3, respectively, and wherein in the formula (4), R⁶, R⁷,and R⁸ each represent hydrogen, an alkyl group having 1 to 20 carbonatoms, a vinyl group, a phenyl group, or a benzyl group, and R⁷ and R⁸may bond and form an aromatic ring; R⁹ represents hydrogen or an alkylgroup having 1 to 3 carbon atoms; R¹⁰ and R¹¹ each represent an alkylgroup having 1 to 5 carbon atoms; and a and p are integers of 1 to 10and 1 to 3, respectively.
 4. A method for producing the organiccarboxylate composition according to claim 2, wherein the basic silanecoupling agent is comprised of one compound or a mixture of two or morecompounds selected from the group consisting of compounds expressed bythe general formulas (1) through (4) below, or at least one selectedfrom the group consisting of amino group-containing silane couplingagents, dialkylamino group-containing silane coupling agents,monomethylamino group-containing silane coupling agents, benzimidazolegroup-containing silane coupling agents, benzotriazole group-containingsilane coupling agents, and pyridine ring-containing silane couplingagents,

wherein in the formulas (1) through (3), R¹, R², and R³ each representhydrogen, a vinyl group, or an alkyl group having 1 to 20 carbon atomsand R² and R³ may form an aromatic ring; R⁴ and R⁵ each represent analkyl group having 1 to 5 carbon atoms; and m and n are integers of 1 to10 and 1 to 3, respectively, and wherein in the formula (4), R⁶, R⁷ andR⁸ each represent hydrogen, an alkyl group having 1 to 20 carbon atoms,a vinyl group, a phenyl group, or a benzyl group, and R⁷ and R⁸ may bondand form an aromatic ring; R⁹ represents hydrogen or an alkyl grouphaving 1 to 3 carbon atoms; R¹⁰ and R¹¹ each represent an alkyl grouphaving 1 to 5 carbon atoms; and o and p are integers of 1 to 10 and 1 to3, respectively.
 5. An epoxy resin composition, containing the organiccarboxylate composition according to claim
 1. 6. An additive for epoxyresin, containing the organic carboxylate composition according to claim1.